Moving Mountains: Reshaping the Activity Volcano of Electrocatalysis with Fluxional Subnano Clusters

16 December 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The activity volcano derived from Sabatier analysis provides intuitive guide for catalyst design, but it also imposes fundamental limitations on the maximal activity and the pool of high-performance elements. Here we show that the activity volcano for oxygen reduction reaction (ORR) can be shifted and reshaped in the subnano regime. The fluxional behavior of subnano clusters, in both isolated and graphite-supported forms, not only breaks the linear scaling relationships but also causes an overall strengthening in adsorbate binding. The metals with optimal adsorbate binding in the bulk form (Pt/Pd) thus suffer over-binding issues, while the metals that under-bind in the bulk form (Ag/Au) gain optimal reaction energetics. In addition, the potential-dependence of isomer energies differ, causing non-linear reaction free energy-potential relations and enabling population-tuning of specific isomers, thereby surpassing the apex of the activity volcano. The shift of the volcano that puts under-binding elements closer to the top is likely general in fluxional cluster catalysis, and can be used for cluster catalyst design.


Cluster catalysis
Sabatier principle
Oxygen reduction reaction

Supplementary materials

Supplementary Information for Moving Mountains: Reshaping the Activity Volcano of Electrocatalysis with Fluxional Subnano Clusters
Isomer distribution of M4 and M4/C systems; Pair-correlation heatmap of adsorbate binding energies with atomic and bulk properties; Free energy-potential curves from GCDFT calculations; Potential-dependent free energy and isomer distributions at 300 K, 1000 K.


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.